U.S. patent number 4,314,058 [Application Number 06/119,147] was granted by the patent office on 1982-02-02 for indolins styryl-like compounds.
This patent grant is currently assigned to Matsushita Electric Industrial Co., Ltd.. Invention is credited to Masaaki Hayami, Seiko Torikoshi.
United States Patent |
4,314,058 |
Hayami , et al. |
February 2, 1982 |
Indolins styryl-like compounds
Abstract
This invention relates to color-changing stryl-like compounds
and the preparing of the same. A compound according to the present
invention has, as its principal ring, an indoline ring of 2nd
position, and has, at stimulation reversible or irreversible
change(s) between a closed ring structre of a non-plane molecular
structure indicated by the following chemical formula(1) showing
white or pale color, and an open ring structure of a plane
molecular structure indicated by the following chemical formula(2)
showing vivid visible color: ##STR1## Wherein Q represents benzene
ring with or without substituted radicals and/or condensed ring(s);
R.sub.1 and R.sub.2 represent lower alkyl radicals hydroxyalkyl
radicals or alkoxyalkyl radicals of the same or different kinds,;
R.sub.3 represents hydrogen, alkyl radical, alkoxy radical,
halogen, nitrile radical, aromatic radical or phenoxy radical; Y
represents oxygen (O) or sulfer (S); Z represents alkylene radical
of carbon number of 2 to 4 with or without alkyl substitution
radical(s) necessary to form a ring structure together with
##STR2## A represents a condensation reaction residue of an
aromatic aldehyde, heterocyclic aldehyde, aromatic nitroso
compound, or heterocyclic nitroso compound. And X represents an
anion.
Inventors: |
Hayami; Masaaki (Okayama,
JP), Torikoshi; Seiko (Okayama, JP) |
Assignee: |
Matsushita Electric Industrial Co.,
Ltd. (Osaka Pref., JP)
|
Family
ID: |
14475603 |
Appl.
No.: |
06/119,147 |
Filed: |
February 6, 1980 |
Related U.S. Patent Documents
|
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
921095 |
May 2, 1978 |
|
|
|
|
734626 |
Oct 21, 1976 |
4147862 |
|
|
|
611834 |
Sep 9, 1975 |
|
|
|
|
Foreign Application Priority Data
|
|
|
|
|
Sep 18, 1974 [JP] |
|
|
49/108090 |
|
Current U.S.
Class: |
544/89; 540/546;
540/547; 544/242; 544/32; 544/333; 546/104; 546/270.1; 546/271.7;
548/121; 548/150; 548/159; 548/181; 548/217 |
Current CPC
Class: |
B41M
5/286 (20130101); C09B 23/105 (20130101); C09B
23/143 (20130101); G03C 8/02 (20130101); G03C
1/29 (20130101); G03C 1/685 (20130101); G03C
1/24 (20130101) |
Current International
Class: |
B41M
5/28 (20060101); C09B 23/00 (20060101); C09B
23/14 (20060101); C09B 23/10 (20060101); G03C
1/08 (20060101); G03C 1/24 (20060101); G03C
1/685 (20060101); G03C 1/12 (20060101); G03C
1/29 (20060101); G03C 8/02 (20060101); C07D
498/04 () |
Field of
Search: |
;260/243.3,244.4,245.6,245.7,245.5 ;544/32,89,242,333 ;546/270
;548/121,159,150,217 ;542/415,401,432,434,455 |
References Cited
[Referenced By]
U.S. Patent Documents
Other References
Chemischerr Informationsdienst 1974, #5-262..
|
Primary Examiner: Demers; Arthur P.
Attorney, Agent or Firm: Cushman, Darby & Cushman
Parent Case Text
This is a continuation application [37 CFR 1.60] of Ser. No.
921,095, filed May 2, 1978, now abandoned which in turn is a
continuation application [37 CFR 1.60] of Ser. No. 734,626, filed
Oct. 21, 1976, now U.S. Pat. No. 4,147,862, said Ser. No. 734,626
being in turn a continuation-in-part of Ser. No. 611,834, filed
Sept. 9, 1975, now abandoned.
Claims
What is claimed is:
1. A compound of the formula ##STR27## wherein Q is aryl;
each of R.sub.1 and R.sub.2 is lower alkyl, hydroxyl alkyl, or
alkoxyalkyl;
R.sub.3 is hydrogen, alkyl, alkoxy, halogen, cyano, aryl, or
phenoxy;
Y is oxygen or sulfur;
Z is alkylene of 2 to 4 carbon atoms unsubstituted or substituted
by alkyl;
A is a condensation reaction residue of a compound selected from
the group consisting of an aryl aldehyde, a nitroso aryl, a
heterocyclic aldehyde compound, and a nitroso indole,
said aryl aldehyde and said nitroso aryl being free of a hydroxy or
a derivative of hydroxy ortho to the carbon atom bonded to said
C.dbd. and said heterocyclic moiety being selected from the group
consisting of indole, furan, thiophene, pyridine, carbazole,
pyrrole, benzothiazole, benzoselenazole, thiazole, benzopyran
quinoline, acridine, and pyrimidine, wherein said heterocyclic
moiety is unsubstituted or substituted by alkyl, alkylidene, aryl,
or halogen.
2. A dye of claim 1, wherein the aromatic nitroso compound is
selected from the group consisting of
p-dimethylaminonitrosobenzene; p-diethylaminonitrosobenzene,
p-methylnitrosobenzene(p-nitrosotoluen), p-nitro-nitrosobenzene,
o-nitronitrosobenzene and 3-nitroso-2-nitrotoluene.
3. A dye of claim 1, wherein the aldehyde of a heterocyclic
compound is selected from the group consisting of furfural,
5-methylfurfural, 5-bromo-furfural, 4-isopropylfurfural,
2-thiophene-carboxaldehyde, 5-methyl-thiophene-carboxaldehyde,
3-methoxybenzothiophene-2-carboxaldehyde, 2-pyridinecarboxaldehyde,
3-pyridinecarboxaldehyde, 4-pyridinecarboxaldehyde,
1-ethylindole-3-carboxaldehyde, 1-methylindole-3-carboxaldehyde,
1-methyl-2-phenylindole-3-carboxaldehyde,
N-methyl-carbazole-2-carboxaldehyde,
N-ethyl-7-bromo-carbazole-2-carboxaldehyde,
N-(n-octyl)-7-nitrocarbazole-2-carboxaldehyde,
benzofuran-2-carboxaldehyde, dibenzofuran-2-carboxaldehyde,
pyrrole-2-aldehyde, N-methylpyrrole-2-aldehyde,
N-phenylpyrrole-2-aldehyde, 3-methylpyrrole-2-aldehyde,
2-ethyl-pyrole-5-aldehyde, benzothiazole-2-aldehyde,
6-methylbenzothiazole-2-aldehyde, 6-chlorobenzothiazole-2-aldehyde,
5-chlorobenzothiazole-2-aldehyde,
6-methoxybenzothiazole-2-aldehyde,
5,6-dichlorobenzothiazole-2-aldehyde, benzoselenazole-2-aldehyde,
6-methoxybenzoselenazole-2-aldehyde,
2,4-dimethylpyrrole-2-aldehyde,
4,6-dichloro-pyrimidine-5-carboxaldehyde,
2-formyl-4,6-dimethylpyrimidine, quinoline-2-aldehyde,
acridine-10-aldehyde
2,4-diphenyl-5,6,7-hexahydrobenzopyran-8-carboxaldehyde and
2,4-diphenyl-6-methyl-5,6,7-pentahydrobenzopyran-8-carboxaldehyde.
4. A dye of claim 1, wherein the nitroso indole compound is
selected from the group consisting of 3-nitrosoindole,
2-methyl-3-nitrosoindole and 3-nitroso-2-phenylindole.
5. The compound of claim 1, wherein said compound undergoes
reversible color change on exposure to light.
6. The compound of claim 1, wherein the aryl of said aryl aldehyde,
said nitroso aryl, and Q is a substituted or unsubstituted
phenyl.
7. The compound of claim 1, wherein the aryl of Q is unsubstituted
phenyl, naphthyl, or phenyl substituted by at least one selected
from the group consisting of acetyl, chloro, methyl, methoxy,
carboethoxy, nitro and iodo.
8. The compound of claim 1, wherein the aryl of said aryl aldehyde
and of said nitroso aryl is unsubstituted phenyl or phenyl
substituted by at least one selected from the group consisting of
dimethyl amino; chloro; nitro; bromo; methoxy; acetyl;
meta-hydroxy; para-hydroxy; methyl, 3,4-dioxy methylene; cyano and
acetylamino.
9. A compound according to claim 1 where R.sub.3 is hydrogen.
10. A compound according to claim 1 where A is a condensation
reaction residue of a compound selected from the group consisting
of an aryl aldehyde, a nitroso aryl, an aldehyde of a compound
selected from the group consisting of unsubstituted or substituted
indole, furyl, thiophene, pyridine, carbazole, pyrrole,
2-benzothiazole, 2-benzoselenazole, 2-thiazole, 8-benzopyrane,
quinoline, acridine and 2-pyrimidine, and a nitroso indole, said
aryl aldehyde and said nitroso aryl being free of a hydroxy or a
derivative of hydroxy ortho to the carbon atom of said compound
bonded to said C.dbd..
11. The compound of claim 10, wherein the aryl of Q is
unsubstituted phenyl, naphthyl, or phenyl substituted by at least
one selected from the group consisting of acetyl, chloro, methyl,
methoxy, carboethoxy, nitro and iodo.
12. The compound of claim 10, wherein the aryl of said aryl
aldehyde and of said nitroso aryl is unsubstituted phenyl or phenyl
substituted by at least one selected from the group consisting of
dimethyl amino; chloro; nitro; bromo; methoxy; acetyl;
meta-hydroxy; para-hydroxy; methyl, 3,4-dioxy methylene; cyano and
acetylamino.
13. The compound of claim 12, wherein the aryl of Q is
unsubstituted phenyl, naphthyl, or phenyl substituted by at least
one selected from the group consisting of acetyl, chloro, methyl,
methoxy, carboethoxy, nitro and iodo.
14. The compound of claim 10, wherein the aryl of Q is
unsubstituted phenyl, naphthyl or phenyl substituted by at least
one selected from the group consisting of halogen, alkyl, alkoxy,
carboalkoxy, amino, acylamino, aryroylamino, dialkylamino,
alkylamino, aryloxy, carboxy, cyano and aryl.
15. The compound of claim 10, wherein the aryl of said aryl
aldehyde and said nitroso aryl is unsubstituted phenyl or phenyl
substituted by dialkylamino; halogen; alkoxy; alkyl; 3,4-dioxy
alkylene or mixtures thereof.
16. The compound of claim 10, wherein the aryl of Q is
unsubstituted phenyl, naphthyl, or phenyl substituted by at least
one selected from the group consisting of acetyl, chloro,
acetamino, methyl, methoxy, carboethoxy, nitro, diethylamino,
dimethylamino and iodo.
17. The compound of claim 10, wherein the aryl of said aryl
aldehyde and of said nitroso aryl is unsubstituted phenyl or phenyl
substituted by a member selected from the group consisting of
dimethylamino, dibutylamino, chloro, nitro, methoxy, bromo,
meta-hydroxy, 3,4-dioxymethylene, acetamino and cyano.
18. The compound of claim 10 which is 3,3-dimethyl-2-{2-(5-chloro
benzothiazolyl)vinyl}indolino[1,2-b]oxazoline.
19. The compound of claim 10, which is
3,3-dimethyl-2-{2-(9-ethyl-7-bromo-carbazolyl)vinyl}indolino[1,2-b]oxazoli
ne.
20. The compound of claim 10, which is
3,3-dimethyl-5-chloro-2-(1-ethyl-3-indolyl
vinyl)indolino-[1,2-b]oxazoline.
21. The compound of claim 10, which is
3,3-dimethyl-5-acetylamino-2-(3-pyridyl
vinyl)indolino[1,2-b]oxazoline.
22. The compound of claim 10, which is 3-methyl-3-ethoxy
ethyl-5-carboxy
ethyl-2-(p-diethylamino-2-azastyryl)indolino[2,1-b]oxazoline.
23. The compound of claim 10, which is
3,3-dimethyl-5-methoxy-2-(p-dimethylamino
styryl)indolino[1,2-b]-1,3-tetrahydro oxazine.
24. The compound of claim 10, which is 3,3-dimethyl-2-(p-chloro
styryl)indolino[1,2-b]-4-methyl oxazoline.
25. The compound of claim 10, which is
3,3-dimethyl-2-(p-dimethylamino-2-methyl
styryl)indolino[1,2-b]oxazoline.
26. A compound of the formula ##STR28## wherein: Q is aryl;
each of R.sub.1 and R.sub.2 is lower alkyl, hydroxy alkyl or
alkoxyalkyl;
R.sub.3 is hydrogen, alkyl, alkoxy, halogen, cyano, aryl or
phenoxy;
Y is oxygen or sulfur;
Z is alkylene of 2 to 4 carbon atoms unsubstituted or substituted
by alkyl;
A is a condensation reaction residue of a compound selected from
the group consisting of an aryl aldehyde, a nitroso aryl, an indole
aldehyde and a nitroso indole,
said aryl aldehyde and said nitroso aryl being free of a hydroxy or
a derivative of hydroxy ortho to the carbon atom of said compound
bonded to said C.dbd..
27. The compound of claim 26 which is
3,3-dimethyl-2-(para-dimethylaminostyryl)indolino-[1,2-b]oxazoline.
28. The compound of claim 26 which is
3,3-dimethyl-5-methoxy-2-(para-chlorostyryl)
indolino-[1,2-b]oxazoline.
29. The compound of claim 26 which is
3,3-dimethyl-5-chloro-2-(para-dimethylaminostyryl)
indolino-[1,2-b]thiazoline.
30. The compound of claim 26 which is
3,3-dimethyl-5-chloro-2-(para-methoxystyryl)
indolino-[1,2-b]-1,3-tetrahydroxyoxazine.
31. The compound of claim 26 which is
3,3-dimethyl-5-chloro-2-(para-dimethylamino-2-azastyryl)
indolino-[1,2-b]oxazoline.
32. The compound of claim 26 which is
3,3-dimethyl-2-(3,4-dioxymethylene styryl)
indolino-[1,2-b]oxazoline.
33. The compound of claim 24, wherein said compound undergoes
reversible color change on exposure to light.
34. The compound of claim 26, wherein the aryl of said aryl
aldehyde, said nitroso aryl, and Q is a substituted or
unsubstituted phenyl.
35. The compound of claim 26, wherein the aryl of Q is
unsubstituted phenyl, napthyl, or phenyl substituted by at least
one selected from the group consisting of acetyl, chloro, methyl,
methoxy, carboethoxy, nitro, iodo and hydroxyethyl.
36. The compound of claim 26, wherein the aryl of said aryl
aldehyde and of said nitroso aryl is unsubstituted phenyl or phenyl
substituted by at least one selected from the group consisting of
dimethyl amino; chloro; nitro; bromo; methoxy; acetyl; hydroxy;
methyl, 3,4-dioxy methylene; and acetylamino.
37. The compound of claim 36 wherein the aryl of Q is unsubstituted
phenyl naphthyl, or phenyl substituted by at least one selected
from the group consisting of acetyl, chloro, methyl, methoxy,
carboethoxy, nitro, iodo and hydroxyethyl.
38. The compound of claim 26, wherein the aryl of Q is
unsubstituted phenyl, naphthyl or phenyl substituted by at least
one selected from the group consisting of keto, halogen, alkyl,
alkoxy, carboalkoxy, nitro and hydroxy alkyl.
39. The compound of claim 38, wherein the aryl of said aryl
aldehyde and said nitroso aryl is unsubstituted phenyl or phenyl
substituted by dialkylamino; halogen; nitro; alkoxy; keto; hydroxy;
alkyl; 3,4-dioxy alkylene, ketoamino, or mixtures thereof.
40. A compound according to claim 26 where R.sub.3 is hydrogen.
Description
BACKGROUND OF THE INVENTION
Spiropyran compounds have been well known as substances which
changes, lose or restore their colors at stimulation by light or
heat. However, the abovementioned known substances have such
shortcomings as necessitating a great amount of energy and not
being sufficiently stable.
SUMMARY OF THE INVENTION
This invention purports to provide novel color-changing compounds
which are stable and require less energy to change, lose or restore
their colors, and the preparing methods of them.
DETAILED DESCRIPTION
The color changing substances of the present invention are
compounds of the below mentioned chemical formula: ##STR3##
Wherein and hereinafter in this invention, Q represents benzene
ring with or without substituted radical(s) and/or condensed
ring(s); R.sub.1 and R.sub.2 represent lower alkyl radicals
hydroxyalkyl radicals or alkoxyalkyl radicals of the same or
different kinds,; R.sub.3 represents hydrogen, alkyl radical,
alkoxy radical, halogen, nitrile radical, aromatic radical or
phenoxy radical; Y represents oxygen (O) or sulfur (S); Z
represents alkylene radical of carbon number of 2 to 4 with or
without alkyl substitution radical(s) necessary to form a ring
structure together with ##STR4## A represents a condensation
reaction residue of an aromatic aldehyde, heterocyclic aldehyde,
aromatic nitroso compound, or heterocyclic nitroso compound.
A first method of preparing the abovementioned compound is
characterized in that an indoline derivative having the following
chemical formula: ##STR5## is reacted with one substance selected
from the group consisting of aromatic aldehydes, heterocyclic
aldehydes, aromatic nitroso compounds and heterocyclic nitroso
compounds, to form styryl-like compounds represented by the
following chemical formula: ##STR6##
A second method of preparing the abovementioned compound is
characterized in that a styryl dye having the following chemical
formula: ##STR7## is reacted with an alkali to form the styryl-like
compound represented by the chemical formula(1), wherein X
represents an anion.
This invention was made through a finding that a 2nd-position
methyl radical or methylene radical of an indoline derivative
represented by the chemical formula(3) is chemically active and
makes dehydrating condensation reaction with aromatic aldehyde,
heterocyclic aldehyde, aromatic nitroso compound or heterocyclic
nitroso compound to form condensation product indicated by the
chemical formula(1).
The abovementioned reaction is obtainable by either of the
following methods:
(1) The abovementioned starting materials (namely, compound of the
chemical formula(3) and an aldehyde or a nitroso compound) are
heated to melt in the presence or in absence of an alkali.
(2) The abovementioned starting materials are heated to react in a
nonpolar solvent.
(3) The abovementioned starting materials are heated to react in an
aprotonic type polar solvent.
(4) The abovementioned starting materials are reacted in the
presence of an alkali in a protonic type solvent.
(5) The abovementioned starting materials are reacted in the
presence of an alkali, in a nonpolar solvent, an aprotonic type
polar solvent or a mixture thereof.
(6) The abovementioned starting materials are reacted in a protonic
type solvent.
Also, the invention was made through another finding that the
abovementioned chemical compound of the chemical formula(1) can be
prepared also by treating the styryl compound of the chemical
formula(2) with an alkali.
When the abovementioned starting materials (i.e., the compound of
formula(3) and the aldehyde or nitroso compound) are treated in the
absence of alkali, in a protonic type solvent, or in a mixed
solvent consisting of a protonic type solvent and at least one
selected from the group of nonpolar solvent and aprotonic type
polar solvent, then the following two cases occur:
(a) Intended compound represented by the chemical formula(1) is
produced, and
(b) A mixture of the intended compound represented by the chemical
formula(1) and by-product (dye) represented by the chemical
formula(2) is produced. From the mixture, the respective compounds
represented by the chemical formulas(1) and (2) can be easily
separated from each other by treating the mixture with a
fractionating solvent such as ether, benzene, ethyl acetate,
n-hexane or cyclohexane.
When the abovementioned indoline-derivative of chemical formula(3)
and the abovementioned aldehyde or nitroso compound are made to
react with each other in the presence of acetic anhydride, acetic
acid or mixture thereof, then styryl dye of indolenium type of
chemical formula(2) is obtainable. In such reaction by adding an
alkali in the mixture of the starting materials or by dissolving
once separated coarse product in a suitable solvent and
subsequently adding an alkali thereto, and by further heating the
mixture, the aimed product indicated by the chemical formula(1) is
prepared.
When the aimed product of the formula(1) and the styryl dyes of
indolenium type are produced, in a form of a mixture thereof, by
the aforementioned reaction between the indoline-derivative and the
abovementioned aldehyde or nitroso compound in a protonic type
solvent or a mixed solvent containing thereof in the absence of
alkali as abovementioned, then the aimed product is obtainable by
adding an alkali into the abovementioned reacting system or a
solution made by dissolving the separated mixture in a suitable
solvent and subsequently heating the reacting system or the
solution.
For the abovementioned alkali, many organic or inorganic alkalis
can be used.
For the organic alkali, triethylamine, piperidine or morpholine is
preferable. For the inorganic alkali, alkali carbonate or ammonia
is preferable.
One example of preparation of the indoline derivative of the
chemical formula(3) is as follows:
A 2-alkyl-indolenine derivative represented by the following
formula ##STR8## and a quaternary-salts agent represented by XZYH,
as the starting materials, are heat-reacted. And the resultant
product represented by the following formula(5) is treated in an
aqueous solution or an organic solvent solution of inorganic alkali
such as caustic soda, sodium carbonate or ammonia, or of organic
alkali such as triethylamine, piperidine or morpholine. ##STR9##
Then, the separated oil-like substance or crystal is further
extracted by means of non-aqueous organic solvent. Then, the
product is dehydrated, and the solvent is evaporated, and the
residue product is crystallized through vacuum distillation or by
means of nonpolar organic solvent.
Further, through another vacuum distillation and crystallization or
precipitation, the indoline derivative represented by the chemical
formula(3) is obtained.
For the starting materials, namely, the indoline derivative of the
formula(3) and an aldehyde or a nitroso compound, any indoline
derivative, any aldehyde or any nitroso compound can be employed
provided that these starting materials enable dehydrating
condensation reaction between methyl radical or methylene radical
of 2nd-position of the indoline derivative and aldehyde radical or
nitroso radical of the aldehyde or nitroso compound. For instance,
for benzene-ring substitution radical to constitute the
indolenine-derivative of the formula(4), alkyl radical, substituted
alkyl radical, alkoxy radical, aryloxy radical, amino, substituted
amino, aryl, substituted aryl, alkoxy carbonyl radical, carboxy
radical, carboxy alkyl radical, nitro radical, cyano radical or
halogen can be employed.
On the other hand, the color-type styryl dyes represented by
formula(2) are also obtainable by condensation-reaction of the
abovementioned product of formula(5) and aromatic aldehydes,
heterocyclic aldehydes or nitroso compounds represented by
Ar--(CH.dbd.CH).sub.n --CHO or Ar--NO (wherein Ar represents
aromatic nucleus or heterocyclic nucleus, n indicates 0 or 1).
For preferable indolenine derivative for the present invention any
of the following can be employed: 2,3,3-trimethyl-indolenine,
2,3,3,5-tetramethyl-indolenine,
2,3,3-trimethyl-4-methoxy-indolenine,
2,3,3-trimethyl-5-methoxy-indolenine,
2,3,3-trimethyl-6-methoxy-indolenine,
2,3,3-trimethyl-7-methoxy-indolenine ,
2,3,3-trimethyl-5-amino-indolenine,
2,3,3-trimethyl-5-acetoamino-indolenine,
2,3,3-trimethyl-5-benzoylamino-indolenine,
2,3,3-trimethyl-5-dimethylamino-indolenine,
2,3,3-trimethyl-5-ethylamino-indolenine,
2,3,3-trimethyl-5-nitro-indolenine,
2,3,3-trimethyl-6-nitro-indolenine,
2,3,3-trimethyl-5-iodo-indolenine,
2,3,3-trimethyl-7-bromo-indolenine,
2,3,3-trimethyl-5-ethoxycarbonyl-indolenine,
2,3,3-trimethyl-5-phenoxy-indolenine,
2,3,3-trimethyl-5-anilino-indolenine,
2,3,3-trimethyl-5-carboxy-indolenine ,
2,3,3-trimethyl-5-cyano-indolenine,
2,3,3-trimethyl-5-phenyl-indolenine,
2,3,3-trimethyl-4,5-benzo-indolenine,
2,3,3-trimethyl-4,5-dimethoxy-indolenine,
2,3,3,5,7-pentamethyl-indolenine,
2,3,3-trimethyl-5,6-dimethoxy-indolenine ,
2,3,3,7-tetramethyl-5-nitro-indolenine,
2-methyl-3,3-diethyl-indolenine, 2,3-dimethyl-3-ethyl-indolenine,
2,5-dimethyl-3,3-diethyl-indolenine,
2,3-dimethyl-3-hydroxyethyl-indolenine,
2,3-dimethyl-3-ethoxymethyl-indolenine and
2,3-dimethyl-3-phenoxyethyl-indolenine. Besides, polycyclic
condensation indolenine such as naphto-indolenine can be employed,
too.
For preferable quaternary salts agent for the present invention,
any of the following can be employed: ethylene bromohydrin, ethylen
chlorohydrin, trimethylene chlorohydrin trimethylene bromohydrin,
tetramethylen chlorohydrin, tetramethylene bromohydrin,
1-chloro-2-propanol, 2-chloro-1-propanol, 2-chloroethyl mercaptan
and 3-chloropropyl mercaptan.
It is empirically found that any of the following aromatic
aldehydes can be used as the aforementioned aromatic aldehyde:
benzaldehyde, p-acetaminobenzaldehyde, p-bromobenzaldehyde,
m-bromobenzaldehyde, o-bromozenzaldehyde,
p-dimethylaminobenzaldehyde, p-diethylaminobenzaldehyde,
p-dibutylamino-benzaldehyde, o-chlorobenzaldehyde,
p-chlorobenzaldehyde, p-anisaldehyde, o-anisaldehyde,
p-tolu-aldehyde, m-tolu-aldehyde, o-tolu-aldehyde,
o-ethoxybenzaldehyde, p-ethoxybenzaldehyde, p-fluorobenzaldehyde,
o-fluorobenzaldehyde, p-nitro-benzaldehyde, m-nitro-benzaldehyde,
o-nitro-benzaldehyde, p-cyanobenzaldehyde, o-cyanobenzaldehyde,
2,4-dichlorobenzaldehyde, 2,6-dichlorobenzaldehyde,
2,4-dichlorobenzaldehyde, 3,5-dichlorobenzaldehyde,
2,4-dimethoxybenzaldehyde, 2,5-dimethoxybenzaldehyde,
3,4-dimethoxybenzaldehyde, 3,5-dimethoxybenzaldehyde,
2,4-dimethylbenzaldehyde, 2,5-dimethylbenzaldehyde,
3,4-dimethylbenzaldehyde, 3,5-dimethylbenzaldehyde,
veratraldehyde(3,4-dimethoxy benzaldehyde),
4-isopropylbenzaldehyde, o-(2-chloroethyl) benzaldehyde,
2,4,6-trimethylbenzaldehyde, 2,4,6-triethoxybenzaldehyde,
3,4-dimethyl-p-anisaldehyde, 2,5-dimethyl-p-anisaldehyde,
2-chloro-5-nitrobenzaldehyde, 2-chloro-6-nitrobenzaldehyde,
2-chloro-3-nitrobenzaldehyde, 5-chloro-2-nitrobenzaldehyde,
vanillin, o-vanillin, isovanillin, 5-bromo-vanillin,
2-chloro-4-dimethylaminobenzaldehyde,
2-chloro-6-fluorobenzaldehyde, 5-bromo-veratraldehyde,
6-bromo-veratraldehyde, 5-bromo-2-methoxy-benzaldehyde,
1-naphto-aldehyde, 2-naphtoaldehyde,
p-dimethylamino-cinnamaldehyde, p-diethylamino-cinnamaldehyde,
p-nitro-cinnamaldehyde, o-nitro-cinnamaldehyde,
.alpha.-chloro-cinnamaldehyde, 2-chloro-cinnamaldehyde,
9-anthraldehyde, 10-chloro-9-anthraldehyde,
9-phenanthrene-carboxyaldehyde and fluorencarboxyaldehyde.
It is empirically found that any of the following aromatic nitroso
compounds can be used as the aforementioned aromatic nitroso
compound: p-dimethylaminonitrosobenzene,
p-diethylaminotrosobenzene,
p-methyl-nitrosobenzene(p-nitrosotoluene) p-nitro-nitrosobenzene,
o-nitro-nitrosobenzene, 3-nitroso-2-nitrotoluene.
It is empirically found that any of the following heterocyclic
aldehydes can be used as the aforementioned heterocyclic aldehyde:
furfural, 5-methylfurfural, 5-bromofurfural, 4-isopropylfurfural,
2-thiophene-carboxaldehyde, 5-methyl-thiophene-carboxaldehyde,
3-methoxybenzothiocitric-2-carboxaldehyde,
2-pyridinecarboxaldehyde, 3-pyridinecarboxaldehyde,
1-methylindole-3-carboxaldehyde,
1-methyl-2-phenylindole-3-carboxaldehyde,
N-methyl-carbazole-2-carboxaldehyde, N-ethyl
-7-bromo-carbazole-2-carboxaldehyde,
N-(n-octyl)-7-nitro-carbazole-2-carboxaldehyde,
benzofuran-2-carboxaldehyde, dibenzofuran-2-carboxaldehyde,
pyrrole-2-aldehyde, N-methylpyrrole-2-aldehyde,
N-phenylpyrrole-2-aldehyde, 3-methylpyrrole-2-aldehyde,
2-ethyl-pyrrole-5-aldehyde, benzothiazole-2-aldehyde,
6-methylbenzothiazole-2-aldehyde, 6-chlorobenzothiazole-2-aldehyde,
5-chlorobenzothiazole-2-aldehyde,
6-methoxybenzothiazole-2-aldehyde,
5,6-dichlorobenzothiazole-2-aldehyde, benzoselenazole-2-aldehyde,
6-methoxybenzoselenazole-2-aldehyde, 4-methylthiazole-2-aldehyde,
3,3-dimethyl-indolenine-2-aldehyde, 2,4-dimethylpyrrole-2-aldehyde,
4,6-dichloro-pyrimidine-5-carboxaldehyde,
2-formyl-4,6-dimethylpyrimidine, quinoline-2-aldehyde,
acridine-10-aldehyde,
2,4-diphenyl-5,6,7-hexahydrobenzopyran-8-carboxaldehyde and
2,4-diphenyl-6-methyl-5,6,7-pentahydrobenzopyran-8-carboxaldehyde,
N-ethyl-benzothiazole-2-pentamethine-.omega.-aldehyde,
3-ethyl-2-formlymethylene-2(3H)thiazolyliden,
1,3,3-trimethyl-2formylmethylene-2(3H)indolyliden,
furan-2-dimethine-.beta.-aldehyde.
It is empirically found that any of the following heterocyclic
nitroso compounds can be used for the aforementioned heterocyclic
nitroso compounds: 3-nitrosoindole, 2-methyl-3-nitrosoindole and
3-nitroso-phenylindole.
In each of the styryl-like compounds produced according to the
present invention, each closed ring exists only on the side of its
indoline ring, and on the right side of methine-chain of
2nd-position carbon, the structure is not on the same plane with
the left side. Namely, the compounds have structures bent at the
methine-chain. Therefore, the lacalized electrons become abundant
in comparison with ordinary indoline dyes wherein the electrons are
not localized. Consequently, in the compounds produced by the
present invention, maximum absorptions can not reach the
wavelengths in visual range, and the maximum absorption lie in
ultraviolet ray range, showing white, transparent or pale yellowish
appearance. The abovementioned compounds change into a plane
structure of indolenium type of formula(2) when their N-Z-Y rings
open.
By selecting the component members, namely indoline derivative and
aldehyde or nitroso compound, various dyes having maximum
absorptions in near ultraviolet range, visible range or in near
infrared range are obtainable. Also, the dyes show various maximum
absorptions when dissolved in various solvents as follows:
3,3-dimethyl-2-(p-dimethylaminostyryl)-indolino-[1,2-b]-oxazoline
298 nm (in n hexane),
547 nm (in methanol),
298 nm (in n-propanol),
298 nm (in n-octyl alcohol),
547 nm (in acetic acid),
299 nm (in acetonitrile-acetic acid),
299 nm (in acetonitrile),
550 nm (in ethanol).
Others of the abovementioned compounds of the present invention
show similar characteristics, wherein the compounds show prominent
red-shift in methanol, ethanol or acetic acid.
Comparison between the compounds of the present invention and
conventional spiropyran compounds, which comparison is used as
photographic or thermal recording material, is elucidated in the
following, so as to clarify advantage of the compounds of the
present invention.
In the present invention, the closed ring structure is formed by
the indoline ring only, while in the conventional
indolino-spiropyrans, a closed ring structure exists between the
indoline ring and benzen ring. This difference gives the compounds
of the present invention a great advantage that an aldehyde or
nitroso compound as starting material can be selected from a wide
variety.
In the conventional indolino-spiropyran compound, it is necessary
to select an aromatic aldehyde or a nitroso compound which has
hydroxyl radical in ortho-position. However, according to the
present invention, such condition is not necessary, but any kind as
well as any structure of the aromatic aldehyde or nitroso compound
can be used, and furthermore, heterocyclic aldehyde or heterocyclic
nitroso compound also can be used.
Moreover, in the conventional indolino spiropyran compound, it is
necessary that the aldehyde radical or the nitroso radical bonds to
the aromatic ring. However, in the present invention such is not
required, and the aldehyde radical or nitroso radical need not bond
directly to the aromatic ring or the heterocyclic ring, but may
bond at the end of conjugate diene bond.
The abovementioned characteristic of the present invention causes
advantage in selection of materials, variety of colors of the
produced dye, and other physical properties. For instance, the
conventional indolino spiropyran compound has a structure that the
indoline ring and the benzen ring are connected by two methine
chains, and therefore, when the structure is changed to open and
show visible color, the number of conjugate double-bond chains is
limited, and consequently, the wavelength of maximum absorption of
the compound is limited at most in the region of 550-580 nm even if
a substitution radical is suitably selected. In another
spiropyrans, there are such shortcomings as the purity of color at
the open-ring structure is not satisfactory, or the changing to the
open-ring structure takes place only in cold temperature. Even in
the indolino spiropyrans which has the purest colors, the variety
of colors is not satisfactory. On the contrary, the abovementioned
compound of the present invention has many a variety of colors
produced by various absorptions near the ultraviolet to near the
infrared regions, and has an advantage of showing various colors in
response to an additive such as solvent.
Also, in applications in photographic field, the styryl-like
compounds of the present invention as well as the indolenium-type
open-ring structure compounds of the formula(2) are useful as optic
sensitizer when used together with various cyanine dyes. The
compounds of the present invention can be used as non-developable
masking film of erasable type of a photographic film. When
contained in a film emulsion of diffusion-transfer type
photographic film, the compounds of the present invention function
to increase the transfer sensitivity and keep the film base clean
even after repetition of the transfer process.
In the following, the present invention is elucidated by means of
many examples, but the compound described in the following examples
are mere representative examples, and therefore, the scope of the
present invention should not be considered as limited to these
examples.
Examples 1 to 15 are for the first method, namely, reacting an
indoline derivative of the formula(3) and an aldehyde or a nitroso
compound.
Examples 16 to 22 are for the second method, namely, treating a
styryl dye of the formula(2) in an alkali.
EXAMPLE 1
3,3-dimethyl-2-(para-dimethylaminostyryl)indolino-[1,2-b]oxazoline
##STR10## was prepared in the following way:
Thirty gram of 2,3,3-trimethyl indolenine and 25 g of ethylene
bromhydrine were heated at 120.degree. C. for 6 hrs. The resultant
viscous solid was refluxed with heating in 100 ml of acetone. The
resultant residue was cooled and filtered to form 38 g of
1-hydroxyethyl-2,3,3-trimethyl indoleniumbromide. Next, 10 g of
1-hydroxyethyl-2,3,3-trimethyl indoleniumbromide was mixed with
sodium carbonate solution. The mixture was extracted with
ethylether. The ethylether-region was separated and washed with
water, and then dehydrated with anhydrous magnesium sulfate and
filtered. The filtrate was evaporated to remove the ethyleter, with
formation of a pale yellow oily substance. By distillating the pale
yellow oily substance under reduced pressure, 2,3,3-trimethyl
indolino-[1,2-b] oxazoline represented by general formula(3) was
obtainable as a colorless oily substance having boiling point of
112.degree. C./6 mmHg.
It was confirmed by means of elemental analysis and nuclear
magnetic resonance spectra, data of which are shown below:
By elemental analysis, Molecular formula was:
C.sub.13 H.sub.17 NO, C:77.22 (theoretical value 76.85) H:8.54
(theoretical value 8.37) N:7.03 (theoretical value 6.90).
By nuclear magnetic resonance spectra (Solvent: CDCl.sub.3,
Reference Sample:Trimethylsilane),
.delta.=1.15 (3H.S. 3--CH.sub.3 or 2--CH.sub.3),
.delta.=1.31 (3H.S. 3--CH.sub.3 or 2--CH.sub.3),
.delta.=1.40 (3H.S. 3--CH.sub.3 or 2--CH.sub.3),
.delta.=3.34-3.89 (4H.m. --CH.sub.2 --CH.sub.2 --),
.delta.=6.66 and 7.00-7.20 (3H.m. Aromatic protones), hence,
Structural formula: ##STR11##
One gram of 2,3,3-trimethyl indolino[1.2-b]oxazoline and 0.75 g of
para-dimethylaminobenzaldehyde were refluxed in 30 ml of absolute
ethanol for 3.0 hours, and then the solvent was removed by
evaporation. The residue was extracted with ethyl ether. The layer
of ethyl ether (ethyl ether containing the extract) was dried with
neutral drying agent such as magnesium sulfate and filtered out.
The filtrate was evaporated to remove the solvent. The resultant
residue was extracted by heating in n-hexane. The mixture was
treated with active carbon and filtered. The filtrate was
evaporated to take away the solvent. The resultant residue was
treated with petroleum ether to obtain 0.35 g of the desired
product, namely a very pale yellowish cream amorphous crystal,
which melts at 142.degree. C. and exhibits its maximum absorption
(in n-hexane) at 296 nm.
EXAMPLE 2
3,3-dimethyl-5-methoxy-2-(para-chlorostyryl)indolino-[1,2-b]oxazoline
##STR12## was prepared in the following way:
2,3,3-trimethyl-5-methoxy indolino[1,2-b]oxazoline 1.1 g and
para-chlorobenzaldehyde 0.7 g were refluxed with boiling in 35 ml
of absolute ethanol for 3.5 hours, and then the ethanol was removed
by evaporation. The resultant pale yellow oily substance was washed
two times with water containing a small quantity of methanol by
decantation and dissolved in small quantities of methanol to be
made basic with ammonia water, followed by dilution with water. The
resultant cream and slightly viscous solid was broken by means of
petroleum ether to crystallize. The formed crystal was extracted by
heating in n-hexane. The mixing was treated with active carbon and
filtered. The filtrate was evaporated to remove the solvent. The
residue was cooled with ice and broken with a small amount of
petroleum ether. The petroleum ether was filtered off with suction.
Upon vacuum-drying the residue, the desired product, namely pale
yellowish-greenish or light yellowish white powdered crystals, was
obtained. The crystals have a melting point of 123.degree. C. and
exhibit their maximum obsorption (in n-hexane) at 258 nm.
EXAMPLE 3
3,3-dimethyl-5-chloro-2-(para-dimethylaminostyryl)-indolino[1,2-b]oxazoline
##STR13## was prepared in the following way:
In 40 ml of absolute ethanol containing 0.3 ml of triethylamine,
1,2 g of 2,3,3-trimethyl-5-chloroindolino-[1,2-b]oxazoline and 0.75
g of para-dimethylaminobenzaldehyde were refluxed by heating for 2
hours, and then the ethanol was eliminated by evaporation. The
resultant residue was washed two times with water by decantation,
further washed well with cold water, filtered, and then extracted
with ethyl ether. The mixture of residue and ethyl was treated with
active carbon and filtered. The filtrate was evaporated to remove
the ethyl ether. The residue was extracted by heating in the
suitable amount of n-hexane. The mixture was then filtered. The
filtrate was evaporated to remove the n-hexane. Upon vacuum-drying
the residue, the desired product, namely pale pinkish white
powdered crystals, was obtained. The crystals have a melting point
of 165.degree. to 166.degree. C. and exhibit their maximum
absorption (in n-hexane) at 299 nm.
EXAMPLE 4
3,3-dimethyl-2-(para-nitrostyryl)indolino[1,2-b]oxazoline ##STR14##
was prepared in the following way:
One gram of 2,3,3-trimethyl-indolino[1,2-b]oxazoline and 0.75 g of
para-nitrobenzaldehyde was refluxed with heating in 35 ml of
benzene for 2,5 hours, and then the benzene was removed by
evaporation. The resultant residue was washed with ethyl ether and
heated with the suitable amount of water to form a crude crystal.
The methanol-insoluble residue of the crude crystal was dissolved
in 5 ml of chloroform. The solution was added to 25 ml of n-hexane
to precipitate the desired product, namely a bright pale yellow
amorphous crystal. The crystal melts at 163.degree. to 164.degree.
C. and exhibits its maximum absorption (in n-hexane) at 294 nm.
EXAMPLE 5
3,3,5-trimethyl-2-(para-dimethylaminostyryl)indolino-[1,2-b]oxazoline
##STR15## was prepared in the following way:
In 30 ml of acetonitrile, 1.1 g of
2,3,3,5-tetramethylindolino[1,2-b]oxazoline and 0.75 g of
para-dimethylaminobenzaldehyde were heated on a water bath for 2
hours, and then the acetonitrile was removed by evaporation under
vacuum. The resultant residue was dissolved in 30 ml of acetone.
The solution was treated with active carbon and filtered. The
filtrate was evaporated to remove the acetone. The residue was
further dissolved in ethyl ether. The solution was treated with
active carbon and filtered. The ethyl ether was removed from the
filtrate by evaporation. The resulting residue was broken by means
of petroleum ether. The petroleum ether was filtered off with
suction. Upon vacuum-drying the residue, the desired product,
namely a pale yellow white powdered crystals, was obtained. The
crystals melt at 170.degree. C. and exhibit their maximum
absorption (in n-hexane) at 297 nm.
EXAMPLE 6
3,3-dimethyl-4,5-benzo-2-(para-dimethylaminostyryl)-indolino[1,2-b]oxazolin
e ##STR16## was prepared in the following way:
On a water bath, 1.28 g of
2,3,3-trimethyl-4,5-benzoindolino[1,2-b]oxazoline and 0.75 g of
para-dimethylaminobenzaldehyde were subjected to a fusion reaction
for 1.5 hours. The reactant was treated with active carbon in 40 ml
of acetone. The region of acetone was filtered off and evaporated.
The residue was cooled with the suitable amount of water to form a
crystal. The crystal was filtered with suction, dried, and then
extracted by heating in n-hexane. The mixture was treated with
active carbon and, next the solvent was removed by evaporation. The
resulting residue was braked with a small quantity of petroleum
ether to form a crystal. The formed crystal was of slightly darkish
cream or pale yellow amorphous one. It melts at 197.degree. C. and
exhibits its maximum absorption (in n-hexane) at 298 nm.
EXAMPLE 7
3,3-dimethyl-2-(metha-bromostyryl)indolino[1,2-b]oxazoline
##STR17## was prepared in the following way:
One gram of 2,3,3-trimethylindolino[1,2-b]oxazoline and 0.92 g of
methabrombenzaldehyde were heated in 30 ml of 1,4-dioxane on a
water bath for 2 hours, and then the solvent was removed by
evaporation. The residue was treated with active carbon in ethyl
ether. Evaporation was carried out to remove the solvent. The
residue was treated with petroleum ether to form a crystal. The
crystal exhibits it maximum absorption (in n-hexane) at 245 nm.
EXAMPLE 8
3,3-dimethyl-5-chloro-2-(para-methoxystyryl)indolino-[1,2-b]oxazoline
##STR18## was prepared in the following way:
In 0.3 ml of trimethylamine, 1.2 g of
2,3,3-trimethyl-5-chloroindolino[1,2-b]oxazoline and 0.68 g of
para-methoxybenzaldehyde were subjected to a fusion reaction on a
water bath for 1.5 hours. The reactant was cooled, washed three to
four times with water, and then extracted with ethyl ether. The
solution was dehydrated by anhydrous sodium sulfate and filtered.
The filtrate was evaporated to remove the solvent and then treated
with a small amount of petroleum ether to form a crystal. The
formed crystal was extracted with n-hexane, treated with active
carbon, and then filtered. The residue was treated with petroleum
ether, with the formation of the desired product, namely a pale
cream-yellow crystal, which melts at 132.degree. C. and exhibits
its maximum absorption (in n-hexane) at 264 nm.
EXAMPLE 9
In accordance with the method of example 1 or 2, the following
compound were prepared by the reaction of one of
2,3,3-triethylindolino[1,2-b]oxazoline derivatives and one of
aromatic aldehydes. In parentheses at each end of compound name,
its melting point (.degree.C) (hereinafter referred to as mp),
maximum absorption (nm) (hereinafter referred to as max a) which is
measured in n-hexane if otherwise mentioned, and in some special
case shoulder absorption (hereinafter referred to as shol a) are
designated. The definition is applied to the subsequent
examples:
3,3-dimethyl-6-methoxy-2-(para-dimethylaminostyryl)-indolino[1,2-b]oxazolin
e (mp: 128.degree. C., max a: 298 nm),
3,3-dimethyl-2-(para-chlorostyryl)indolino[1,2-b]oxazoline (mp:
91.degree. to 92.degree. C., max a: 259 nm),
3,3,5-trimethyl-2-(para-chlorostyryl)[1,2-b]oxazoline (mp:
141.degree. to 142.degree. C., max a: 258 nm),
3,3-dimethyl-2-(para-acetylaminostyryl)indolino[1,2-b]oxazoline
(mp: 197.degree. C., max a: 280 nm),
3,3-dimethyl-2-(para-hydroxystyryl)indolino[1,2-b]oxazoline (mp:
125.degree. to 127.degree. C., max a: 260 nm),
3,3,5-trimethyl-2-(para-nitrostyryl)indolino[1,2-b]oxazoline (mp:
164.degree. to 165.degree. C., max a: 298 nm),
3,3-dimethyl-5-methoxy-2-(para-methoxystyryl)indolino[1,2-b]oxazoline
(mp: 111.degree. to 112.degree. C., max a: 268 nm),
3,3-dimethyl-2-(metha-methoxystyryl)indolino[1,2-b]-oxazoline (mp:
102.degree. to 104.degree. C., max a: 253 nm),
3,3-dimethyl-2-(ortho-methylstyryl)indolino[1,2-b]oxazoline (mp:
79.degree. to 80.degree. C., max a: 244 nm) and
3,3-dimethyl-2-(ortho-chlorostyryl)indolino[1,2-b]oxazoline (mp:
84.degree. to 85.degree. C., max a: 244 nm).
In addition, in accordance with the method of example 1 or 2, the
following compounds were prepared by the reaction of one of
2,3,3-trimethylindolino[1,2-b]-1,3-tetrahydroxazine derivatives and
one of aromatic aldehydes.
3,3-dimethyl-2-(para-dimethylaminostyryl)indolino[1,2-b]-1,3-tetrahydroxazi
ne (mp: 132.degree. to 134.degree. C., max a: 299 nm) and
3,3-dimethyl-5-chloro-2-(para-methoxystyryl)indolino[1,2-b]-1,3-tetrahydrox
azine (mp: 143.degree. C., max a: 233 nm).
Next, the following compounds were prepared by the reaction of one
of cinnamaldehydes and one of indoline derivatives:
3,3-dimethyl-5-methoxy-2-(para-dimethylaminocinnamilidenevinyl)indolino[1,2
-b]oxazoline (mp: 135.degree. C., max a: 326 to 328 nm),
3,3-dimethyl-2-(para-dimethylaminocinnamilidenevinyl)indolino[1,2-b]oxazoli
ne (mp: 166.degree. C., max a: 328 to 332 nm),
3,3-dimethyl-5-chloro-2-(para-dimethylaminocinnamilidenevinyl)indolino[1,2-
b]oxazoline (mp: 179.degree. C., max a: 338 to 340 nm),
3,3-dimethyl-2-(para-diethylaminocinnamilidenevinyl)indolino[1,2-b]oxazolin
e (max a: 326 to 330 nm),
3,3-dimethyl-2-(para-dimethylaminocinnamilidenevinyl)indolino[1,2-b]-1,3-te
trahydroxazine (max a: 328 to 331 nm),
3,3-dimethyl-5-chloro-2-(para-dimethylaminocinnamilidenevinyl)indolino[1,2-
b]-1,3-tetrahydroxazine (max a:337 to 340 nm),
In addition, in accordance with the method of Example 1 or 2, the
following compounds were prepared by the reaction of one of
aromatic aldehydes and one of 2,3,3 trimethyl-indolino[1,2-b]
thiazoline:
3,3-dimethyl-5-methoxy-2-(para-dimethylaminostyryl)indolino[1,2-b]thiazolin
e (mp: 121.degree. to 123.degree. C., max a: 398 to 400 nm (in
acetone)),
3,3-dimethyl-5-carboethoxy-2-(3,4-methylene
dioxystyryl)indolino[1,2-b]thiazoline (mp: 117.degree. to
119.degree. C., max a: 366 nm),
3,3-dimethyl-5-chloro-2-(para-methylstyryl)indolino[1,2-b]thiazoline
(mp: 57.degree. to 59.degree. C., max a:350 to 352 nm),
3,3-dimethyl-5-chloro-2-(para-methoxystyryl)indolino[1,2-b]thiazoline
(max a: 352 to 353 nm),
3,3,5-trimethyl-2-(para-acetylaminostyryl)indolino[1,2-b]thiazoline
(mp: 123.degree. to 125.degree. C., max a: 356 to 358 nm),
3,3-dimethyl-5-methoxy-2-(3-hydroxy-4-methoxystyryl)indolino[1,2-b]thiazoli
ne (max a: 358 to 378 nm) and
3,3-dimethyl-5-carboethoxy-2-(ortho-cyanostyryl)indolino[1,2-b]thiazoline
(mp: 54.degree. to 55.degree. C., max a: 269 to 271 nm).
In addition, the following compounds were prepared by the reaction
of one of heterocyclic aldehydes and one of indoline
derivatives:
3,3-dimethyl-2-{2-(5-methylfuryl)vinyl}indolino[1,2-b]oxazoline
(max a: 277 nm, shol a: 288 to 289 nm),
3,3-dimethyl-5-chloro-2-{2-(thienyl)vinyl}indolino[1,2-b]oxazoline
(mp: 107.degree. to 109.degree. C., max a: 247 nm and 284 nm)
and
3,3-dimethyl-2-{2-(9-methylcarbazolyl)vinyl}indolino[1,2-b]oxazoline
(mp: 77.degree. to 79.degree. C., max a: 242 to 244 nm and 285
nm).
EXAMPLE 10
In accordance with the processing of example 3 or the modification,
the following compounds were prepared by the reaction of one of
2,3,3-trimethylindolino[1,2-b]oxazoline,
2,3,3-trimethylindolino[1,2-b]-1,3-tetrahydroxazine or
2,3,3-trimethylindolino[1,2-b]thiazoline derivatives and one of
aromatic or heterocyclic aldehydes:
3,3-dimethyl-5-methoxy-2-(para-dimethylaminostyryl)indolino[1,2-b]oxazoline
(mp: 132.degree. C., max a: 297 nm),
3,3-dimethyl-7-methoxy-2-(para-dimethylaminostyryl)indolino[1,2-b]oxazoline
(mp: 134.degree. C., max a: 294 nm),
3,3-dimethyl-5-nitro-2-(para-methoxystyryl)indolino[1,2-b]oxazoline
(mp: 167.degree. C., max a: 264 nm, shol a: 327 nm),
3,3-dimethyl-2-(3,4-dioxymethylenestyryl)indolino[1,2-b]oxazoline
(mp: 81.degree. to 82.degree. C., max a: 271 nm, shol a: 293
nm),
3,3-dimethyl-5-methoxy-2-(para-methoxystyryl)indolino[1,2-b]-1,3-tetrahydro
xazine (mp. 97.degree. to 99.degree. C., max a: 264 nm),
3,3-dimethyl-2-(metha-methylstyryl)indolino[1,2-b]oxazoline (max a:
246 nm),
3,3-dimethyl-5-chloro-2-(para-ethoxystyryl)indolino[1,2-b]-oxazoline
(max a: 264 to 265 nm),
3,3-dimethyl-2-(3,4-dichlorostyryl)indolino[1,2-b]oxazoline (max a:
256 to 258 nm),
3,3-dimethyl-2-{2-(5-chlorobenzothiazolyl)vinyl}-indolino[1,2-b]ozazoline
(max a: 235 to 236 nm, shol a: 280 to 281 nm),
3,3-dimethyl-5-chloro-2-{2-(benzoselenazolyl)vinyl}-indolino[1,2-b]oxazolin
e (max a: 244 to 245 nm, shol a: 295 to 296 nm),
3,3-dimethyl-2-{2-(furyl)-1,3-butadienilidene}-indolino[1,2-b]oxazoline
(max a: 285 to 287 nm),
3,3,5-trimethyl-2-(para-dimethylaminostyryl)indolino[1,2-b]thiazoline
(mp: 96.degree. to 98.degree. C., max a: 385 to 386 nm),
3,3,5-trimethyl-2-(para-chlorostyryl)indolino[1,2-b]-thiazoline
(mp: 68.degree. to B 69.degree. C., max a: 346 nm, shol a: 358
nm),
3,3,5-trimethyl-2-{2-(thienyl)vinyl}indolino[1,2-b]thiazoline (max
a: 359 to 360 nm) and
3,3-dimethyl-5-methoxy-2-{2-(9-ethylcarbazolyl)vinyl}-indolino[1,2-b]thiazo
line (mp: 104.degree. to 106.degree. C., max a: 381 nm, shol a: 364
to 366 nm).
EXAMPLE 11
The following compounds were prepared by the reaction of one of
2,3,3-trimethylindolino [1,2-b]oxazoline derivatives and one of
aromatic aldehydes in accordance with the processing of example 4
of the modification:
3,3-dimethyl-5-iodo-2-(para-dimethylaminostyryl)indolino[1,2-b]oxazoline
(mp: 169.degree. C., max a: 294 nm),
3,3-dimethyl-5-chloro-2-(para-nitrostyryl)indolino[1,2-b]oxazoline
(mp: 132.degree. to 133.degree. C., max a: 297 nm),
3,3-dimethyl-5-nitro-2-(para-nitrostyryl)indolino[1,2-b]oxazoline
(mp: 217.degree. C., max a: 308 nm),
3,3-dimethyl-2-styrylindolino [1,2-b]oxazoline and
3,3-dimethyl-5-chloro-2-(3,4-dimethoxystyryl)indolino[1,2-b]oxazoline
(max a: 266 nm).
EXAMPLE 12
The following compounds were prepared by the reaction of one of
2,3,3-trimethylindolino [1,2-b]ozazoline or
2,3,3-trimethylindolino[1,2-b]thiazoline derivatives and one of
aromatic aldehydes in accordance with the method of example 5 or
the similar processing:
3,3,5-trimethyl-2-(para-methoxystyryl)indolino[1,2-b]oxazoline (mp:
127.degree. to 128.degree. C., max a: 264 nm),
3,3-dimethyl-2-(para-dimethylaminostyryl)indolino[1,2-b]thiazoline
(mp: 116.degree. to 117.degree. C., max a: 400 nm),
3,3-dimethyl-5-carbo
ethoxy-2-(para-dimethylaminostyryl)indolino[1,2-b]thiazoline (mp:
101.degree. to 103.degree. C., max a: 403 nm) and
3,3-dimethyl-2-(para-dibutylaminostyryl)indolino[1,2-b]oxazoline
(mp: 72.degree. to 73.degree. C., max a: 300 to 302 nm).
The following compounds were prepared by the reaction of one of
aromatic nitroso compounds and one of indoline derivatives:
3,3-dimethyl-2-(para-dimethylamino-2-azastyryl)indolino[1,2-b]oxazoline
(mp: 72.degree. to 75.degree. C., max a: 290 to 292 nm) and
3,3-dimethyl-5-chloro-2-(para-dimethylamino-2-azastyryl)indolino[1,2-b]oxaz
oline (mp: 140.degree. C., max a: 303 to 304 nm).
EXAMPLE 13
The following compounds were prepared by the reaction of one of
2,3,3-trimethylindolino[1,2-b]oxazoline or
2,3,3-trimethylindolino[1,2-b]-1,3-tetrahydroxazine derivatives and
one of aromatic or heterocyclic aldehydes in accordance with the
processing of example 6 or the modification:
3,3-dimethyl-5-methoxy-2-(para-chlorostyryl)indolino[1,2-b]oxazoline
(mp: 118.degree. C., max a: 258 nm),
3,3-dimethyl-5-chloro-2-(para-dimethylaminostyryl)indolino[1,2-b]-1,3-tetra
hydroxazine (mp: 153.degree. to 154.degree. C., max a: 306 nm),
3,3-dimethyl-4,5-benzo-2-(para-dimethylaminostyryl)indolino[1,2-b]-1,3-tetr
ahydroxazine (mp: 96.degree. to 97.degree. C. max a: 304 nm)
and
3,3-dimethyl-5-methoxy-2-{2-(4-methylthiazolyl)vinyl}indolino[1,2-b]oxazoli
ne (max a: 238 to 239 nm, shol a: 296 to 298 nm).
EXAMPLE 14
The following compounds were prepared by the reaction of one of
2,3,3-trimethylindolino[1,2-b]oxazoline,
2,3,3-trimethylindolino[1,2-b]-1,3-tetrahydroxazine or
2,3,3-trimethylindolino[1,2-b]thiazoline derivatives and one of
aromatic aldehydes, aromatic nitroso compounds and heterocyclic
aldehydes in accordance with the method of example 7 or the
modified processing:
3,3-dimethyl-5-nitro-2-(para-dimethylaminostyryl)indolino[1,2-b]oxazoline
(mp: 193.degree. C., max a: 302 nm, shol a: 325 nm),
3,3-dimethyl-5-metoxy-2-(para-nitrostyryl)indolino[1,2-b]oxazoline
(mp: 172.degree. to 173.degree. C., max a: 301 nm),
3,3-dimethyl-2-(2,4-dimetoxystyryl)indolino[1,2-b]oxazoline (max a:
265 to 267 nm),
3,3-dimethyl-2-(metha-nitrostyryl)indolino[1,2-b]oxazoline (mp:
122.degree. to 123.degree. C., max a: 244 nm),
3,3-dimethyl-2-(3-pyridylvinyl)indolino[1,2-b]oxazoline (max a: 243
to 244 nm, shol a: 284 to 286 nm),
3,3-dimethyl-2-(1-ethyl-3-indolylvinyl)indolino[1,2-b]oxazoline
(max a: 234 to 235 nm, shol a: 263 to 264 nm, 287 to 288 nm),
3,3-dimethyl-2-(3,3-dimethyl-2-indolylvinyl)indolino[1,2-b]oxazoline
(max a: 237 to 238 nm, shol a: 284 to 285 nm),
3,3-dimethyl-2-{2-(9-ethyl-7-bromocarbazolyl)vinyl}indolino[1,2-b]oxazoline
(mp: 88.degree. to 89.degree. C., max a: 289 nm, shol a: 299
nm),
3,3-dimethyl-5-chloro-2-{2-(benzothiazolyl)vinyl}indolino[1,2-b]thiazoline
(mp: 131.degree. to 132.degree. C., max a: 259 to 260 nm),
3,3-dimethyl-5-chloro-2-(para-chlorostyryl)indolino[1,2-b]-1,3-tetrahydroxa
zine (mp: 155.degree. C., max a: 259 nm),
3,3-dimethyl-2-(para-chlorostyryl)indolino[1,2-b]-1,3-tetrahydroxazine
(max a: 261 nm),
3,3-dimethyl-5-methoxy-2-(para-dimethylamino-2-azastyryl)indolino[1,2-b]oxa
zoline (mp: 56.degree. to 58.degree. C., max a: 271 to 273 nm),
3,3-dimethyl-5-chloro-2-(para-dimethylamino-2-azastyryl)indolino[1,2-b]-1,3
-tetrahydroxazine (max a: 302 to 303 nm),
3-methyl-3-ethoxymethyl-2-(para-dimethylaminostyryl)-indolino[1,2-b]-1,3-te
trahydroxazine (max a: 294 to 296 nm) and
3-methyl-3-phenoxyethyl-2-(para-dimethylaminostyryl)indolino[1,2-b]oxazolin
e (max a: 296 nm).
EXAMPLE 15
The following compounds were prepared, in accordance with the
processing of example 8 or the modification, by the reaction of one
of 2,3,3-trimethylindolino[1,2-b]oxazoline or
2,3,3-trimethylindolino[1,2-b]-1,3-tetrahydroxazine derivatives and
one of aromatic or heterocyclic aldehydes:
3,3-dimethyl-5-methoxy-2-(para-dimethylaminostyryl)indolino[1,2-b]-1,3-tetr
ahydroxazine (mp: 115.degree. to 116.degree. C., max a: 300
nm),
3,3-dimethyl-2-(para-diethylaminostyryl)indolino[1,2-b]oxazoline
(max a: 302 nm),
3,3-dimethyl-2-{2-(5,6-dimethylbenzothiazolyl)-vinyl}indolino[1,2-b]oxazoli
ne (max a: 237 to 238 nm, shol a: 283 to 284 nm),
3,3-dimethyl-2-{8-(2,4-diphenyl-6-methyl-5,6,7-pentahydrobenzopyranyl)vinyl
}indolino[1,2-b]oxazoline (mp: 96.degree. to 97.degree. C., max a:
260 to 262 nm, shol a: 239 to 242 nm, 340 to 342 nm),
3,3-dimethyl-2-(2-benzothiazolylidenepropylidene)indolino[1,2-b]oxazoline
(max a: 282 to 283 nm, shol a: 350 to 352 nm),
3,3-dimethyl-2-{2-(3,3-dimethylindonilidene)propylidene}indolino[1,2-b]oxaz
oline (max a: 279 to 280 nm),
3-methyl-3-hydroxyethyl-2-(metha-methoxystyryl)-indolino[1,2-b]oxazoline
(max a: 251 to 252 nm),
3,3-dimethyl-2-{2-methyl-(para-dimethylamino)styryl}indolino[1,2-b]oxazolin
e (max a: 292 to 293 nm),
3,3-dimethyl-5-chloro-2-(para-dimethylaminostyryl)indolino[1,2-b]-5-methylo
xazoline (max a: 298 to 300 nm) and
3,3-dimethyl-2-(para-chlorostyryl)indolino[1,2-b]-4-methyloxazoline
(max a: 258 to 260 nm).
EXAMPLE 16
3,3-dimethyl-2-(para-dimethylaminostyryl)indolino[1,2-b]oxazoline
##STR19## was prepared in the following way:
In 30 ml of absolute ethanol, 1.4 g of
1-hydroxyethyl-2,3,3-trimethyl-indoleniumbromide and 0.7 g of
para-dimethylaminobenzaldehyde were refluxed with heating for 3.5
hrs, and then ethanol was eliminated by evaporation. After cooling
with ice and washing with ethylether, the resultant residue was
filtered off as a crude crystal which was
1-hydroxyethyl-3,3-dimethyl-2-(para-dimethylaminostyryl)-indoleniumbromide
. The crude crystal was dissolved into 30 ml of methanol followed
by addition of 5 ml of 57% aqueous hydrogen iodide. After heating
for about three minutes, the mixture was cooled with ice. The
resultant crystal was filtered off and washed well with water, and
then washed with an organic solvent such as mixture of ethylether
and acetone. The resultant crude crystal was recrystallized with
alcohol to obtain 1.5 g of known
1-hydroxyethyl-3,3-dimethyl-2-(para-dimethylaminostyryl)-indoleniumiodide
of a bright purplish blue needles in a 78% yield. Structural
formula was: ##STR20##
Melting point: 222.degree.-223.degree. C.
Maximum absorption: (in H.sub.2 O) 550 nm
Maximum absorption: (in Methanol) 547 nm
Maximum absorption: (in Dichloroethane) 564 nm.
In 15 ml of methanol, 0.5 g of
1-hydroxyethyl-3,3-dimethyl-2-(para-dimethylaminostyryl)indoleniumiodide
(mp: 222.degree. to 223.degree. C., max a (in water): 550 nm,
bright purple or indigo blue needles) was dissolved with heating.
The solution was refluxed in 10 ml of 28% ammonia water for 5 to 10
minutes and evaporated to remove the solvent. The residue was mixed
with 10 ml of 28% ammonia water, diluted with 100 ml of water, and
then cooled with ice. The resultant crystal was taken out by
filtration and sufficiently washed with water. The resultant pale
yellowish cream-white amorphous crystal with negative halogen
reaction was evaporated with heating with 30 ml of ethyl ether and
filtered to remove any insoluble parts. The filtrate was evaporated
to take off the solvent. By the extraction of the residue with
heating with 30 ml of n-hexane, 0.3 g of pale yellowish cream
amorphous crystal identical with one of Example 1 was obtained. It
melts at 142.degree. C. and exhibits its maximum absorption (in
n-hexane) at 296 nm.
EXAMPLE 17
3,3-dimethyl-5-methoxy-2-(para-chlorostyryl)indolino[1,2-b]oxazoline
##STR21## was prepared in the following way:
In 60 ml of water, 1.2 g of
1-hydroxyethyl-3,3-dimethyl-5-methoxy-2-(para-chlorostyryl)indoleniumiodid
e (mp: 239.degree. C., max a (in water): 543 nm, red brown purple
granular needles) was dissolved with heating. Upon cooled and mixed
with 12 ml of 28% ammonia water, the solution became faded and
milky turbid. The resulting crystal was separated from the solution
by filtration, washed well with water, dried, and then extracted
with ethyl ether. The solvent was next eliminated by evaporation
and the residue was extracted with heating with cyclohexane. After
removing the solvent by evaporation, the residue was washed with
petroleum ether with the formation of 0.8 g of the desired product,
namely a pale pinkish yellow white amorphous crystal. It melts at
132.degree. to 133.degree. C. and exhibits its maximum absorption
(in n-hexane) at 258 nm.
EXAMPLE 18
3,3-dimethyl-5-chloro-2-(para-dimethylaminostyryl)-indolino[1,2-b]thiazolin
e ##STR22## was prepared in the following way:
One gram of
1-mercaptoethyl-3,3-dimethyl-5-chloro-2-(para-dimethylaminostyryl)indoleni
umchloride (mp: 237.degree. to 238.degree. C., max a: 538 to 540
nm, light purple granules) was dissolved with heating in 20 ml of
chloroform. The solution was mixed with 1.5 ml of triethylamine and
evaporated to remove the solvent. The residue was extracted with
heating with n-hexane. The n-hexane-insoluble parts were eliminated
from the mixture by filtration. After evaporating the filtrate to
take away the solvent, the residue was washed with petroleum ehter
with the formation of 0.65 g of the desired product, namely orange
yellow granules, which melt at 114.degree. to 115.degree. C. and
exhibit their maximum absorption (in n-hexane) at 408 to 410
nm.
EXAMPLE 19
3,3,5-trimethyl-2-(para-chlorostyryl)indolino[1,2-b]oxazoline
##STR23## was prepared in the following way:
One gram of
1-hydroxyethyl-3,3,5-trimethyl-2-(parachlorostyryl)indoleniumiodide
(mp: 225.degree. C., max a (in water): 400 nm, yellowish orange
needles) was dissolved by heating in 30 ml of methanol, mixed with
0.6 ml of morpholine, and then boiled for 2 minutes. After
evaporating the solution to take away the solvent, the residue was
broken in water, filtered to remove the water, treated with
methanol-ammonia water, filtered again, dried, and then extracted
with ethyl ether. After eliminated the solvent by evaporation, the
residue was extracted by heating in n-hexane. The resultant crystal
weighed 0.6 g of the desired product, namely cream yellow powdered
crystals. The crystals melt at 141.degree. to 142.degree. C. and
exhibit their maximum absorption (in n-hexane) at 258 nm.
EXAMPLE 20
3,3-dimethyl-5-chloro-2-(para-methoxystyryl)indolino[1,2-b]-1,3-tetrahydrox
yoxazine ##STR24## was prepared in the following way:
One gram of
1-hydroxypropyl-3,3-dimethyl-5-chloro-2-(para-methoxystyryl)indoleniumiodi
de (mp: 177.degree. to 178.degree. C., max a (in water): 430 nm,
orange-red granules) was dissolved in 20 ml of dimethylformamide,
heated with 0.5 ml of piperidine for 2 to 3 minutes, cooled, broken
with a suitable amount of water, and then filtered. The residue was
extracted with ethyl ether, dried by anhydrous magnesium sulfate,
and then filtered. The region of ether in the filtrate was treated
with active carbon and filtered. The filtrate was evaporated to
remove the solvent. The resultant residue was extracted with
heating in n-hexane to obtain 0.55 g of the desired product, namely
a dark pale pinkish yellowish white amorphous crystal. It melts at
143.degree. C. and exhibits its maximum absorption (in n-hexane) at
263 nm.
EXAMPLE 21
3,3-dimethyl-5-chloro-2-(para-dimethylamino-2-azastyryl)indolino[1,2-b]oxaz
oline ##STR25## was prepared in the following way:
In 60 ml of methanol, 1.2 g of
1-hydroxyethyl-3,3-dimethyl-5-chloro-2-(para-dimethylamino-2-azastyryl)ind
oleniumbromide (max a (in methanol): 601 nm, bright golden or light
green scales) was dissolved by heating and treated in ammonia water
to separate a creamy crystal. The crystal was filtered out, washed
with water and then vacuum dried. The resultant crystal weighed 0.9
g of the desired product, namely a grayish white amorphous crystal,
melting at 176.degree. C. Upon treating it with n-hexane, a pale
blue-grayish white powder was formed. It melts at 180.degree. C.
and exhibits its maximum absorption (in n-hexane) at 303 nm.
EXAMPLE 22
3,3-dimethyl-2-(3,4-dioxymethylenestyryl)indolino[1,2-b]oxazoline
##STR26## was prepared in the following way:
One gram of
1-hydroxyethyl-3,3-dimethyl-2-(3,4-dioxymethylenestyryl)indoleniumbromide
(mp: 160.degree. to 161.degree. C., max a (in water): 439 nm, shol
a: 270 nm, light orange granules) was dissolved in 30 ml of 20%
methanol-aqueous, added to 15 ml of 5% potassium carbonate aqueous
solution, and then extracted with ethyl ether. The ethyl ether,
after drying by anhydrous sodium sulfate, was filtrated. The region
of ether in the filtrate was removed by evaporation. The residue
was treated with n-hexane to obtain 0.5 g of the desired product,
namely a pink-yellowish yellow-white crystal melting at 80.degree.
to 81.degree. C. and exhibiting its maximum absorption (in
n-hexane) at 271 nm and sholder absorption at 293 nm.
In the abovementioned Examples 16 to 22, disclosure is made on
preparing of several typical examples of the products of the
formula (1) by the second method, namely, treating a styryl dye of
the formula (2) in an alkali. Of course, the compounds prepared by
the Examples 1 to 15 can be prepared by the second method
exemplified in the Examples 16 to 22.
* * * * *